Kinetic study of the interaction of three glycine‐containing dipeptides with diaquaethylenediamineplatinum(II) in aqueous medium

The kinetics of the interaction of three glycine‐containing dipeptides, namely, glycine‐L‐leucine (Gly‐Leu), glycine‐L‐isoleucine (Gly‐Ile), and glycine‐valine (Gly‐Val) with [Pt(en)(H₂O)₂](ClO₄)₂ has been studied spectrophotometrically as a function of [substrate complex], [dipeptides] and temperature at a particular pH(4.0), where the substrate complex exists predominantly as the diaqua species and the dipeptides as a zwitterion. The substitution reaction shows two consecutive steps; the first is the ligand‐assisted anation and the second is the chelation step. The activation parameters for both the steps were evaluated using Eyring's equation. The low ΔH₁^≠ and large negative value of ΔS₁^≠ as well as ΔH₂^≠ and ΔS₂^≠ indicate an associative mode of activation for both the aqua ligand substitution processes. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 498–506, 2011     

First-principles modeling of unpassivated and surfactant-passivated bulk facets of wurtzite CdSe: a model system for studying the anisotropic growth of CdSe nanocrystals

Equilibrium geometries, surface energies, and surfactant binding energies are calculated for selected bulk facets of wurtzite CdSe with a first-principles approach. Passivation of the surface Cd atoms with alkyl phosphonic acids or amines lowers the surface energy of all facets, except for the polar 000 facet. On the nonpolar facets, the most stable configuration corresponds to full coverage of surface Cd atoms with surfactants, while on the polar 0001 facet it corresponds only to a partial coverage. In addition, the passivated surface energies of the nonpolar facets are in general lower than the passivated polar 0001 facet. Therefore, the polar facets are less stable and less efficiently passivated than the nonpolar facets, and this can rationalize the observed anisotropic growth mechanism of wurtzite nanocrystals in the presence of suitable surfactants.     

Synthesis and structural characterisation of CdS nanoparticles prepared in a four-components "water-in-oil" microemulsion

Nanostructured semiconductor particles are currently under intense investigation because of their enhanced photoreactivity and photocatalytic properties due to the quantum-size effect and the dependence of the photophysical and photochemical properties on their size as it approaches the exciton diameter. This increasing interest has led to the development of several synthetic procedures to prepare and stabilise uniform crystallites. In this paper, we report a novel synthetic pathway to obtain cadmium sulphide (CdS) nanoparticles in a quaternary "water-in-oil" microemulsion formed by a cationic surfactant cetyltrimethylammonium bromide (CTAB), pentanol, n-hexane and water. The synthesis of CdS in this system is achieved by mixing two microemulsions containing Cd(NO3)2 and Na2S, respectively. The nanocrystals have been characterised by using UV--visible spectroscopy and Transmission Electron Microscopy to investigate the influence of various parameters of the particles' formation and stability in solution. Capping of nanoparticles with suitable organic molecules has been performed in order to increase their stability and afford solubility in a wide range of solvents.     

Hydrodynamic and thermal interactions of a cluster of solid particles in a pool of liquid of different Prandtl numbers using two-fluid model

The knowledge of thermal interaction between hot particles and liquid is essential for many engineering applications. The main focus of the present study is to understand the underlying phenomena of transient interaction between the hot particles and the liquid of varying Prandtl number under different parametric conditions. Analysis is carried out numerically using in-house multiphase code based on Eulerian two-fluid laminar model. The code is validated against existing results. The dispersion and penetration characteristics of the particles are observed to be a strong function of Prandtl number as well as volume fraction and particle diameter, with a stronger mushrooming observed for lower particle size or high Prandtl number liquid. The thermal interaction is observed to be between the particles and the narrow thermal envelope surrounding the particles. The particles cooling rate are observed to be several orders faster in a liquid with lower Prandtl number.     

Magnetism in FeNiW disordered alloys: Experiment and theory

We report here an experimental study of magnetization of FeNiW alloys at different compositions. We have studied variation of magnetization with temperature (at low external fields) and magnetic field (at low temperatures). The alloy shows para to ferromagnetic transitions across the composition range. We do not find any indication of the spin-glass phase. We have supplemented the experimental work with theoretical analysis using the first-principles tight-binding linear muffin-tin orbitals based augmented space recursion method. Our theoretical estimates of magnetic moment and Curie temperatures agree well with experiment. Our mean-field phase analysis also does not indicate the possibility of a spin-glass phase.     

Cascade synthesis of selective dihydro pyridazino fused acridinone derivatives via MCM-41 catalyzed ring-opening/ring-closure reaction

An enhanced one-pot synthesis of new functionalized 5,6-dihydro-5,5-dimethyl-2-phenyl-2H-pyridazino[3,4,5-kl]acridin-1(4H)-one derivatives with different substituted patterns by using mesoporous MCM-41 catalyst via a ring opening/ring closure reaction process has been established. This MCM-41 silica catalyst has been synthesized and characterized using an array of sophisticated analytical techniques like BET, XRD, UHRTEM, etc. This reaction could be conducted from inexpensive substrates within short period under neat reflux conditions. Compared with the usual methods, the remarkable advantages of this method are milder reaction conditions, operational simplicity, higher yields, short reaction times and an environmentally friendly procedure.     

Graphene as a reversible spin manipulator of molecular magnets

One of the primary objectives in molecular nanospintronics is to manipulate the spin states of organic molecules with a d-electron center, by suitable external means. In this Letter, we demonstrate by first principles density functional calculations, as well as second order perturbation theory, that a strain induced change of the spin state, from S=1→S=2, takes place for an iron porphyrin (FeP) molecule deposited at a divacancy site in a graphene lattice. The process is reversible in the sense that the application of tensile or compressive strains in the graphene lattice can stabilize FeP in different spin states, each with a unique saturation moment and easy axis orientation. The effect is brought about by a change in Fe-N bond length in FeP, which influences the molecular level diagram as well as the interaction between the C atoms of the graphene layer and the molecular orbitals of FeP.     

On the extendedness of eigenstates in a hierarchical lattice: A critical view

We take a critical view at the basic definition of extended single particle states in a non-translationally invariant system. For this, we present the case of a hierarchical lattice and incorporate long range interactions that are also distributed in a hierarchical fashion. We show that it is possible to explicitly construct eigenstates with constant amplitudes (normalized to unity) at every lattice point for special values of the electron-energy. However, the end-to-end transmission, corresponding to the above energy of the electron in such a hierarchical system depends strongly on a special correlation between the numerical values of the parameters of the Hamiltonian. Keeping the energy and the distribution of the amplitudes invariant, one can transform the lattice from conducting to insulating simply by tuning the numerical values of the long range interaction. The values of these interactions themselves display a fractal character.